Effect of phenol end functional switching segments on the shape memory properties of epoxy‐cyanate ester system

The effect of phenol end functional shape memory oligomers on the shape memory properties of an epoxy‐cyanate ester resin system was examined. The basic resin system consisted of diglycidyl ether of bisphenol A (DGEBA) cured with bisphenol A dicyanate (BADC). For conferring the shape memory properties, the switching segment (SS) components selected are α, ω‐phenol‐terminated poly(tetramethyleneoxide) (PPTMO), poly(ε‐caprolactone) (PPCL), and poly(propylene glycol) (PPPG). Epoxy‐cyanate ester blend of defined composition was analyzed for thermal, mechanical, thermo‐mechanical, and shape memory properties at two concentrations of the three SSs. The transition temperature of heavily SS loaded matrix increased in the order: PPTMO < PPCL < PPPG commensurate with crystallizability of SS segments at ambient. For same reason flexural property showed an increasing trend. This is in league with the increased crystallizability of the shape memory polymer components. The shape fixity, recovery extent, and recovery time followed a reverse order: PPPG < PPCL < PPTMO. In contrast to the alcohol terminated shape memory components, phenol terminal groups were helpful in integrating the shape memory segments into the matrix by way of reaction with both epoxy and cyanate groups. The coreaction was conducive for achieving better shape memory properties and decreasing the transition temperature. A direct relation existed between the modulus ratio and the shape recovery property. Higher concentration of the SSs caused a diminution in transition temperature but enhanced the shape memory properties, though the mechanical properties were adversely affected. The shape recovery increased with increase in temperature. All polymers possessed good mechanical properties and thermal stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41196.     

Meticulous analysis and consequences of microstructure changes on melt rheology and dynamic viscoelasticity of thermoplastic vulcanizates upon reprocessing

Thermoplastic vulcanizates (TPVs), which are a special class of elastomer alloy, prepared by dynamic vulcanization possess unique morphology of finely dispersed micron‐size cross‐linked elastomeric particles in a continuous thermoplastic matrix. The present study investigates the microstructure formation of elastomeric phase and its associated morphological changes during reprocessing of TPVs based on poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock co‐polymer (S‐EB‐S) and solution polymerized styrene butadiene elastomer (S‐SBR) by scanning electron microscopy and atomic force microscopy. Semi‐efficient and efficient sulfur‐based curing systems have been adopted to cure the elastomeric phase and a comparative study has been made to demonstrate and explain the effect of reprocessing on the melt rheology and dynamic viscoelasticity of the TPVs. The present work also provides a better insight and guidance to control the microstructure of the cross‐linked elastomeric phase to prepare selectively co‐continuous or dispersed phase morphology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41182.     

Photo-mediated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reactions for forming polymer networks as shape memory materials

The formation of polymer networks polymerized with the Copper (I) – catalyzed azide – alkyne cycloaddition (CuAAC) click reaction is described along with their accompanying utilization as shape memory polymers. Due to the click nature of the reaction and the synthetic accessibility of azide and alkyne functional-monomers, the polymer architecture was readily controlled through monomer design to manipulate crosslink density, ability for further functionalization, and the glass transition temperature (55–114 °C). Free strain recovery is used to quantify the shape memory properties of a model CuAAC network resulting in excellent shape fixity and recovery of 99%. The step growth nature of this polymerization results in homogenous network formation with narrow glass transitions ranges having half widths of the transition close to 15 °C for these materials resulting in shape recovery sharpness of 3.9%/°C in a model system comparable to similarly crosslinked chain growth polymers. Utilization of the CuAAC reaction to form shape memory materials opens a range of possibilities and behaviors that are not readily achieved in other shape memory materials such as (meth) acrylates, thiol-ene, thiol-Michael, and poly(caprolactone) based shape memory materials.     

Effect of Processing on the Physico-Chemical Characteristics of Quinoa Flour (Chenopodium quinoa,Willd)

The nature and extent of the modification of starch in quinoa, caused by various processes like cooking and autoclaving of the seeds, drum drying of the flour and extrusion of the grits was investigated by measuring the physico-chemical properties - the water absorption, water solubility, swelling power, viscosity and degree of gelatinisation - of the processed samples. Autoclaved samples showed the lowest degree of gelatinisation (32.5% by DSC) of the starch, while the degree of gelatinisation of the precooked/drum dried samples was found to be 97.4% by DSC method. Higher polymer degradation was observed in cooked samples than in autoclaved samples as seen in the gel chromatographic separation. The water solubility in cooked samples (5.44 to 15.58) and in autoclaved samples (7.02 to 9.64) increased with the process time. In the extrusion process, the moisture content as well as the compression ratio was found to affect the degree of starch modification significantly (p <0.01).     

Low-Temperature Sintering of La(Ca)CrO3 Powder Prepared through the Combustion Process

Ultrafine La(Ca)CrO₃ (LCC) powder was prepared through the glycine–nitrate gel combustion process. It was shown for the first time that the use of relatively inexpensive CrO₃ as a starting material for chromium has potential for the bulk preparation of sinter-active LCC powder. As-prepared powder, when calcined at 700°C, resulted in LCC along with a small amount of CaCrO₄. The calcined powder was found to be composed of soft agglomerates with a particle size of ≈70–290 nm. The cold pressing and sintering of the calcined powder at 1200°C resulted in the mono-phasic La_0.7Ca_0.3CrO₃ with density ≈98% of its theoretical value. This is the lowest sintering temperature ever reported for La_0.7Ca_0.3CrO₃. The conductivity of the sintered La_0.7Ca_0.3CrO₃ at 1000°C was found to be ≈57 S/cm in air. The sintering and electrical behavior achieved for La_0.7Ca_0.3CrO₃ may find application as an interconnect material for high-temperature solid oxide fuel cells if problems with chemical expansion and poor conductivity in fuel can be overcome.     

Phenolic‐epoxy matrix curable by click chemistry—synthesis,curing, and syntactic foam composite properties

Alkyne functional phenolic resin was cured by azide functional epoxy resins making use of alkyne‐azide click reaction. For this, propargylated novolac (PN) was reacted with bisphenol A bisazide (BABA) and azido hydroxy propyloxy novolac (AHPN) leading to triazole‐linked phenolic‐epoxy networks. The click cure reaction was initiated at 40–65°C in presence of Cu₂I₂. Glass transition temperature (Tg) of the cured networks varied from 70°C to 75°C in the case of BABA‐PN and 75°C to 80°C in the case of AHPN‐PN. DSC and rheological studies revealed a single stage curing pattern for both the systems. The cured BABA‐PN and AHPN‐PN blends showed mass loss above 300°C because of decomposition of the triazole rings and the novolac backbone. Silica fiber‐reinforced syntactic foam composites derived from these resins possessed comparable mechanical properties and superior impact resistance vis‐a‐vis their phenolic resin analogues. The mechanical properties could be tuned by regulating the reactant stoichiometry. These low temperature addition curable resins are suited for light weight polymer composite for related applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41254.     

Effect of co‐solvents on the photovoltaic performance of an inverted organic solar cell

We investigated the effect of varying polymer crystallinity, morphology, and optical property, produced by adding four different co‐solvents in to the poly(3‐hexylthiophene) (P3HT): [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) active layer blend solution, on the functioning of an inverted polymeric solar device. Photovoltaic devices primed with cyclohexanone co‐solvent showed the best performance with power conversion efficiency (PCE) reaching a value of 3.01 ± 0.04%. Improvement in efficiency is related to an increase in photocurrent which is due to a combined result of ordered P3HT crystallite growth, as well as of the precise size and phase separation of domains. POLYM. ENG. SCI., 55:1382–1388, 2015. © 2015 Society of Plastics Engineers     

Hydrogen generation in a Pd membrane fuel processor: Productivity effects during methanol steam reforming

Performance analyses are carried out for the palladium membrane fuel processor for catalytic generation of high purity hydrogen. The reactor model includes detailed particle-scale multi-component diffusion, multiple reversible reactions, flow, and membrane transport. Using methanol steam reforming on Cu/ZnO/Al₂O₃ catalyst as the test reaction, a systematic examination of the effects of operating and reactor design parameters on key performance metrics is presented. Single particle simulations reveal a complex interplay between nonisobaric transport and the reversible reactions (methanol reforming and decomposition, and water-gas shift), which impact overall reactor performance. An analysis of characteristic times helps to identify four different productivity controlling regimes: (i) permeation control, encountered with thick membranes and/or insufficient membrane area; (ii) catalyst pore diffusion control encountered with diffusion of reacting species in larger particles; (iii) reaction control, encountered when intrinsic catalytic rates are too low because of inadequate activity or catalyst loading; and (iv) feed control, encountered when the limiting reactant feed rate is inadequate. The simulations reveal that a maximum in the hydrogen productivity occurs at an intermediate space velocity, while the hydrogen utilization is a decreasing function of space velocity, implying a trade-off between productivity and hydrogen utilization. The locus of productivity maxima itself exhibits a maximum at an intermediate membrane surface to volume ratio, the specific value of which is dependent on the particle size, membrane thickness and reaction conditions. At moderate temperature and total pressure (, 10 bar), particles smaller than 2 mm diameter, Pd membranes with thickness less than , and membrane surface to volume ratio exceeding are needed to achieve viable productivity . A comparison between the packed-bed membrane reactor and conventional packed-bed reactor indicates a modest improvement in the conversion and productivity due to in situ hydrogen removal.     

中国沉积盆地结构类型与成油期规律

中国沉积盆地可分为单层结构箕状断陷型，双层结构断拗型，多层结构，台，断，拗，型实践证明，不论单层，双层，多层结构含油气盆地，一般说来，箕状断陷发育的中期为主要的成油期，多层结构的含油气盆地，台型构造层发育期为最佳成气期。     

Factors Affecting the Stability of CdTe/CdS Solar Cells Deduced from Stress Tests at Elevated Temperature

CdTe/CdS solar cells were subjected to heat stress at 200 °C in the dark under different environments (in N₂ and in air), and under illumination (in N₂). We postulate that two independent mechanisms can explain degradation phenomena in these cells: i) Excessive Cu doping of CdS: Accumulation of Cu in the CdS with stress, in the presence of Cl, will increase the photoconductivity of CdS. With limited amounts of Cu in CdS, this does NOT affect the photovoltaic behavior, but explains the crossover of light/dark current–voltage (J–V) curves. Overdoping of CdS with Cu can be detrimental to cell performance by creating deep acceptor states, acting as recombination centers, and compensating donor states. Under illumination, the barrier to Cu cations at the cell junction is reduced, and, therefore, Cu accumulation in the CdS is enhanced. Recovery of light‐stress induced degradation in CdTe/CdS cells in the dark is explained by dissociation of the acceptor defects. ii) Back contact barrier: Oxidation of the CdTe back surface in O₂/H₂O‐containing environment to form an insulating oxide results in a back‐contact barrier. This barrier is expressed by a rollover in the J–V curve. Humidity is an important factor in air‐induced degradation, as it accelerates the oxide formation. Heat treatment in the dark in inert atmosphere can stabilize the cells against certain causes of degradation, by completing the back contact anneal.